Water-soluble urea resins



Patented Mar. 28, 1950 WATER-SOLUBLE UREA RESINS V Willard L. Morgan, Haverford, 2a., assignor to Arnold, Hofiman & Co. Incorporated, a corporation of Rhode Island 1 No Drawing. Application May 9, 1946,

- Serial No. 668,483

This application is a continuation in part of my application Serial No. 581,329, filed March 6, 1945, which is a continuation in part of my application Serial No. 508,955 filed November 4, 1943.

which is a continuation in part of my application Serial No. 380,887 filed February 27, 1941. All the above applications are now abandoned.

Stable resinous products that are water soluble and at the same time cheap and readily available have considerable uses in the arts as adhesives, binders, plasticizers, as compositions for use in coatings, back-filling and many other types of work in the paper and textile industries.

In the textile industry fabric constructions have in the past been sized by the application of starch, gelatin, and water soluble gum compositions for the purpose of applying coatings which cement down the extraneous fibers on the surface of the yarns or fabric and thereby give a greater smoothness and uniformity of appearance. In the case of warp sizing, it is particularly essential that a good surface film be prepared in order to have acceptable conditions for weaving. Proper binding of the starch is necessary to eliminate fly, breaking of the yarns and subsequent stopping of the looms. In such compositions there is also subsequently used fatty type softeners along with hygroscopic agents which are added to increase the amount of moisture retained in the starch during processing.

In U. S. Patent #1,953,741 to Bennett, July 15, 1932, water soluble resinous products have been made by reaction of glycols or polyhydric alcohols, such as ethylene glycol, diethylene glycol,

etc., by reacting these with boric acid. While such products are water soluble, they have found only limited uses due to their unstability in particular, and water solutions soon after preparation become cloudy and turbid due to boric acid rapidly hydrolyzing and splitting out of the compound. The resin rapidly hydrolyzes and is soon completely destroyed, thereby limiting the utility of these products.

I have found that stable water soluble resins may be prepared which may be kept for a long time in water solutioli'without hydrolysis by reacting boric acid with compounds characterized by containing an amino group. Boric acid is an inorganic acid and while its formula is generally given as, H3303, it is not considered to react as a polybasic acid and upon heating it to relatively low temperatures, it easily gives up one molecule of water and thereafter reacts according to the general formula for metaboric acid (H1302) Its reactions in aqueous solutions have been frequently shown by physical chemical measure- 0. All

2 ments to indicate the formula HBO: rather than HJBOIQ- The organic esters of boric ac indicate an acid or composition HBO-z rather than H3303. All chemical information indicates that boric acid HaBOs is really a hydrate of the acid H1302, and is to be looked upon as HBOz-HzO.

In carrying out the invention, I beat at to 200 0., one or more mols of boric acid with urea or a substituted urea of the following general formula:

In this formula, 2 is a small integer of values from 0 to 3, and in which R. is a group of the following type:

Where s and t are small integers in which 3 varies in which m, n and p are small integers, with n varying from 2 to 6 p from 0 to 6 and m from 2 to 3. Resins made from reactions from these types are all found to be thermoplastic, and vary from soft to hard consistency. The resins which are made from ureas where the two X's become hydrogens are not suitable as textile sizing ingredients, inasmuch as these forms are invariably hard and brittle.

Suitable amino compounds for condensing with urea, forming various substituted ureas which may be then reacted with boric acid to secure water soluble resins, are as follows: monoethanolamine, diethanolamine, mono and di-isopropanolamine, ethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine, heptaethylene octamine, hexapropylene heptamine, hexamethylene diam'ine, 2-amino-2-ethyl-l,3 propanediol, 2- amino-2-methyl-l-propanol, 2-amino-2-methyl- 1,3-propanediol, trimethylol amino methane, 2- amino-2-methyl-l-butanol, 2-amino-1-pentanol and hydroxy ethyl ethylene diamine.

The complex polyamino compounds, such as heptaethylene octamine, hexapropylene heptamine and other similar long chain compounds, may be easily synthesized by reaction of alkyl dihalides and organic amines or other known observed at 110-115 C. and after. hour at 130- C. one mole of ammonia was split out. The temperature was raised to 150 C. in order to remove the last traces of ammonia, at which point monoethanol urea was obtained. Various amines may be substituted for the monoethanolamine illustrated above, either a mono or'a di substituted urea being obtained depending up n the proportion oi urea to amineused.

It is not necessary that the two X's be alike. Suitable urea compounds for condensations with boric acid to secure water soluble resins are as follows:

NHr-E-NHI Urea 0 HOCHSCHINH-ENHI Honoethanol urea O NHs-CHsCHt-NH--NH:

Monobeta amino ethyl urea o Nm- -Nncmom-Nncmcmon Hydroxy ethyl ethylene amino carbamlde 0 HICHiCHsNH-CECHa-NH&NHI

Diethylene diamine carbamide 2-methyl, Z-carbunide l-propenol C H: CHiOH-(-CH1OH NH i=0 I'm,

Z-methyl, 2-carbamide 1,3-propanedlol CHsOE CHIOE-(J-ClIiOH in: 6:0 is.

Z-methylol, 2-carbamide 1-3 propanediol H li-CIIzCHiOH =0 z'w-cmcmon Symmetrical diethanol urea amp 0 NHr-CHsCHg-NH5NHCH|CKPNH8 Symmetrical dibeta amino ethyl urea 0 O NHI-E-NH(CHI)O-NH-ENHCH1CHIOH 1-beta ethanol urea, G-urea, hexane NHCHrCHsNHCHiCHiOH CBICHlNHCHIOHlOH Symmetrical hydroxy ethyl ethylene amine carbamide I HaN-JJ-NHCHaCHa- NH--NH: Ethylene dicarbamide The detailed practice of the invention is illustrated by the following examples wherein the parts are given by weight:

Example 1.62 parts of boric acid (1 mol) were mixed with 104 parts (1 mol) of monoethanol urea and gradually heated until water was collected in the sidearm tube. Heating was continued until C., at which point two mols of water were split out and the residue in the flask cooled down. This yielded a water soluble viscous resin which was soft, practically colorless or slightly yellow, transparent, and slightly bygroscopic in nature. The resin is readily soluble in water and from such aqueous solutions the resin can be again secured by drying down, thus indicating that the product is stable and does not hydrolyze. The water solutions can be kept without any apparent cvidenceot change. The resin is easily softened on heating and is permanently (N'HzCHzCHzNHCONHCHaCHzNHz) (1 mol) prepared by heating two mols of ethylene diamine and one moi of urea at temperatures between 100-150 C. for one half hour at the end of which two mols of ammonia had been liberated, were mixed with 62 parts of boric acid (1 mol) and gradually heated until water was collected in the sidearm tube. Heating was continued until C., at which point two mols of water were split out and the residue in the flask cooled down. This yielded a hard, white to amber resin, water soluble and nonhygroscopic in nature. The resin is readily soluble in water and from such aqueous solutions the resin can be again secured by drying down, thus indicating that the product is stable and does not hydrolyze. The water solutions can be kept without any apparent evidence of change.

Example 3.-62 parts of boric acid (1 mol) were mixed with 148 parts of 2-methyl, Z-carbamide, 1,3 propanediol Hocm0 mrcomm HOCH: CH:

(1 mol) and gradually heated until water was collected in the sidearm tube. Heat was continued until 195 C. at which point two mols of water were split out and the residue in the flask cooled down. This yielded a hard, red resin, water soluble. transparent and nonhygroscopic in nature. The resin is readily soluble in water and from such aqueous solutions the resin can again be secured by drying down, thus indicating that the product is stable and does not hydrolyze. The water solutions can be kept without any apparent evidence of change. The resinis easily softened on heating and is permanently thermoplastic.

6 added body and stiifnesa by running the fabric through a bath containing of corn dextrin dissolved in 100 gallons of water along with 5# of the above described water soluble resin.

Example 7.-62 parts of boric acid (1 mol) were mixed with 261 parts (1 mol) of a poly aikyl amino substituted urea having the following formula:

Rayon yarns sized in a bath containing a solution of 4% gelatin and 1% of the above described water soluble resin were satisfactory for weaving, showing good strength and little fly.

Example 4.-146 parts of ethylene diamine dicarbamide (NHzCONHCHzCHaNHCONH-a) (1 mol) were mixed with 62 parts of boric acid (1 mol) and gradually heated until water was collected in the sidearm tube. Heating was continued until 180 C., at which point 1 mols of water were split out and the residue in the flask cooled down. This residue yielded a water soluble, hard, white resin, nontransparent and hygroscopic in nature. The resin is' readily soluble in water and such solutions can be kept without any evidence of change.

Example 5.-62 parts of boric acid (1 mol) were mixed with 362 parts (1 mol) of an alkyl polyamino substituted urea 01' the following formula:

added after which the temperature was slowly raised to 150 C., ammonia being liberated and the substituted urea obtained. The resinous condensation obtained was light amber, transparent and nonhygroscopic in nature. It was easily water soluble and from such aqueous solutions the resin can be again secured by drying down, thus indicating that the product is stable and does not hydrolyze. The resin itself is easily softened .on heating and is permanently thermoplastic.

Ezample 8.62 parts of boric acid (1 mol) 0 O 0 I II NHa--NHCHsCHr-NH-C-NHCHaCflz-NH-lL-NHCHzCHa-NH- E-NHCHICHIOH and gradually heated to 140 C., at which point 2 mols of water were split out and the residue were mixed with 319 parts (1 mol) of a poly alkyl substituted urea of the following formula:

in the flask cooled down. The aikyi polyamino substituted urea was obtained b heating equimolar quantities of monoethanol urea and symmetrical dibeta amino ethyl urea for one half hour at 130-140 C. during which time one moi of ammonia was liberated. The mixture was then cooled to 100 C. and one mol of ethylene diamine dicarbamide added and the temperature slowly raised to 150 C., ammonia being liberated and the substituted urea indicated in the above formula secured. The resin obtained was Heating was continued until 140-150 C., at

which point 2 mols of water were split out and the flask cooled down to room temperature. The l-beta ethanol urea, G-urea hexane was prepared by heating equimolar quantities of monoethanolurea and hexamethylene diamine to 130-140 C. during which time 1 mol of ammonia was liberated. The mixture was then cooled to 100 C. and 1 mol of urea added, the batch temperature then being slowly raised to 150 C. during which one mol of ammonia was liberated and the substituted urea indicated above was secured. The resin obtained was watersoluble, slightly yellow and transparent in nature. Its water solutions were stable over long periods of time, indicating no hydrolysis on storage.

Printed draperies may be flnished and given an and gradually heated until water was collected in the sidearm tube. Heating was continued until 180 C., at which point 2 mols of water were split out and the residue in the flask cooled. The substituted urea was obtained by the same procedure as in Example 7 with the exception that tetraethylene pentamine was substituted for dipropylene triamine. This yielded a hard, practically water white resin, water soluble, transparent and nonhygroscopic in nature. The water solutions can be kept without any apparent evidence of change.

In sizing sewing threads and twines, it is essential to secure a hard smooth surface which at the same time is flexible. Threads and twines sized with a composition prepared by boiling gallons of water, 50# of tapioca dextrin, 10# of talc and 10# of the water soluble resin described above, gave a very satisfactory sized thread and twine.

Example 9.-62 parts of boric acid (1 mol) weremixed with 405 parts (1 mol) of a poly alkyl substituted urea of the following formula:

. I O NHP -NH -(CH:CHr-NH)| -NHCHaCHzOH and gradually heated until water was evolved. Heating was continued until C. was reached, at which point approximately 2 mols of water were split out and the residue in the flask cooled. The substituted urea was obtained by the same procedure as in Example 7 with the exception that hexaethylene heptamine was substituted on an equimolar basis for dipropyiene triamine. The resin obtained was readily water soluble and 7 stable for storage. The condensate was hard. transparent and nonhygroscopic in nature.

Example 10.--174 parts of a substituted urea, obtained by condensing at temperature between 125-135 C. equal molar quantities of urea and dipropylene triamine. were mixed with 62 parts of boric acid (1 mol) and gradually heated until water was evolved. Heating was continued until 180 C., at which point 1% mols of water were split out and the residue cooled. This yielded a water soluble viscous resin, light yellow, transparent and slightly hygroscopic. The resin is readily soluble in water and from such aqueous solutions may be again secured by drying down, thus indicating that the product is stable and does not hydrolyze. I

Cotton cloth may be satisfactorily back-sized by impregnating the cloth or fabric through a ouetch, squeeze roll and drying machine in which the sized solution is made up by .boiling in 100 gallons of water 130# of corn starch, 225# of talc, 50# saponified tallowand 20# of the above described water soluble resin. The cotton fabric thus back-filled or sized possesses a firm finish in which the starch does not dust off due to the binding characteristics of the water soluble resin.

Example 11.-203 parts (1 mol) of a substituted urea of the following formula:

were mixed with 62 parts (1 mol) boric acid and heated to 160 C. at which point 2 mols of water were split out and the residue in the flask cooled to room temperature. The substituted urea indicated above was obtained by heating equimolar quantities of monoethanolurea and hexamethylene diamine at temperatures between 130-140 C. for one half hour during which time ammonia was liberated. The resin obtained was practically water white, transparent and slightly hygroscopic in nature. It is easily water soluble and from such aqueous solutions no boric acid hydrolyzes under long standing.

Example 12.62 parts of boric acid (1 mol) were mixed with 362 parts (1 mol) of a poly amino alkyiol substituted urea of the following formula:

hexaethylene heptamine and monoethanolurea at temperatures between 130-135 C. during which time 1 mol of ammonia was liberated. This yielded a water soluble, viscous resin, light yellow and transparent. The water solutions are stable with no boric acid hydrolyzing on standing.

Example 13.-62 parts of boric acid (1 mol) were mixed with 276 parts (1 mol) of a polyamino alkylol substituted urea of the following formula:

and gradually heated in a flask until water was collected in the sidearm tube. Heating was continued to 175 C., at which point 2 mols of water were split out and the residue cooled. The polyarnino alkyiol substituted urea indicated above 8 was obtained by heating equimolar quantities of tetraethylene pentamino and monoethsnolurea for one half hour at 130-135 C. during which time one mol of ammonia was liberated. This yielded a water soluble, viscous resin, light yellow and transparent. The water solutions are stable with no boric acid hydrolyzing on standing.

Example 14.-145 parts (1 mol) of -amino amyl urea were mixed with 82 parts (1 mol) of boric acid and heated to 170 0.. at which point 2 mols of water were split out and the residue in the flask cooled. The resinous condensation obtained was practically water white. viscous, transparent and nonhygroscopic in nature. Its water solutions are stable on long standing and from such aqueous solutions a resinous film may again be secured by evaporation.

The above examples are given only by way of illustrations, and the use of various other substituted alkyl ureas carrying hydroxyl or amino groups result in various similar types of resinous products. In view of the fact that water and some ammonia are split out by the reaction of boric acid with either amino or hydroxyl groups, it is to be presumed that the resinous products are formed in this manner. It is apparent that the high polymeric chain resins formed must be rather complex chemical formulas and it is not our intention in offering these suggested reactions as the source of the water and ammonia eliminated that this is the only type wherein z is a small integer of values from 0 to 3 and R is a group (CHa)z--[NH(CH:):]iwhere s and t are small integers with s ranging from 0 to 5 and t from 2 to 6 and X is a radical selected from the group consisting of hydrogen,

in which m, 11. and p are small integers with 1:

varying from 2 to 6, p from 0 to 6 and m from so 2 to 3.

2. The process for forming a water soluble resin by condensing equimolar quantities of boric acid and monoethanol urea at temperatures between 100 and 200 C.

3. The process for forming a water soluble resin by condensing equimolar quantities of boric acid and hydroxy ethyl ethylene amino carbamide at temperatures between 100 and 200 C.

4. The process-for forming a water soluble resin by condensing equimolar quantities of boric acid and 2-methyl-2-carbamide l-propanol at temperatures between and 200 C.

5. A water soluble resinous condensation product of reactants secured by condensing at tem- 76 perature of from 100 to 200 C. equimolar quantities of boric acid and a compound of the following general formula:

wherein z is a small integer of values from to 3 and R is a group -(CH2) -[NH(CH2) i]; where s and t are small integers in which 8 varies from 0 to 5 and t from 2 to 6 and X represents a radical selected from the group consisting of hydrogen,

in which m, n and p are small integers with n varying from 2 to 6, p from 0 to 6 and m from 2 to 3.

6. A water soluble resinous condensate of equimolar quantities of boric acid and monoethanol urea, condensed at temperatures between 100 and 200 C.

7. A water soluble resinous condensate of equimolar quantities of boric acid and hydroxy ethyl ethylene amino carbamide formed by condensing at temperatures between 100 and 200 C.

8. A water soluble resinous condensate of equimolar quantities of boric acid and 2-methyl-2- carbamide l-propanol formed by condensing at temperatures between 100 and 200 C.

9. Textile material sized with a composition in which the binder consists of a water soluble resin secured by the reaction at temperatures of from 100 to 200 C. equimolar quantities of boric acid and a compound of the following general formula:

" where s and t are small integers in which s varies from 0 to 5 and t from- 2 to 6 and X represents a radical selected from the group consisting of hydrogen,

in which m, n and p are small integers with n varying from 2 to 6, p from 0 to 6 and m from 2 to 3.

10. Textile material sized with a composition in which the binder consists 01 a water soluble resin secured by the reaction of equimolar quantitles of boric acid and monoethanol urea at temperatures between and 200 C.

11. Textile material sized with a, composition in which the binder consists of a water soluble resin secured by the reaction of equimolar quantities of boric acid and hydroxy ethyl ethylene amino carbamide at temperatures between 100 and 200 0. I

12. Textile material sized with a composition in which the binder consists of a water soluble resin secured by the reaction of equimolar quan titles of boric acid and 2-methyl-2-carbamlde 1- propanol at temperatures between 100 and WILLARD L. MORGAN.

No references cited. 

1. THE PROCESS FOR THE MANUFACTURE OF WATER SOLUBLE RESINS WHICH CONSISTS OF CONDENSING AT TEMPERATURES OF 100* TO 200*C. EQUIMOLAR QUANTITIES OF BORIC ACID AND A COMPOUND OF THE FOLLOWING GENERAL FORMULA: 